EP0637321B1 - Utilisation de copolymerisats d'acides carboxyliques et de composes a chaines longues a liaisons multiples c-c isolees comme epaississants ou comme dispersants - Google Patents

Utilisation de copolymerisats d'acides carboxyliques et de composes a chaines longues a liaisons multiples c-c isolees comme epaississants ou comme dispersants Download PDF

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EP0637321B1
EP0637321B1 EP93911463A EP93911463A EP0637321B1 EP 0637321 B1 EP0637321 B1 EP 0637321B1 EP 93911463 A EP93911463 A EP 93911463A EP 93911463 A EP93911463 A EP 93911463A EP 0637321 B1 EP0637321 B1 EP 0637321B1
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esters
mono
copolymers
acid
weight
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EP0637321A1 (fr
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Christian Schade
Axel Sanner
Hans-Ulrich Wekel
Franz Frosch
Horst Westenfelder
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BASF SE
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BASF SE
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8164—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof

Definitions

  • the present invention relates to the use of copolymers of carboxylic acids, long-chain compounds with isolated C-C multiple bonds and optionally further copolymerizable monomers and crosslinking agents as thickeners or dispersants, for example in cosmetic or pharmaceutical preparations and cosmetic or pharmaceutical preparations containing these copolymers. Since some of the copolymers are new substances, the invention further relates to these new copolymers.
  • Copolymers of olefinically unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid or maleic anhydride and hydrophobic comonomers such as (meth) acrylic acid esters, ⁇ -olefins with 2 to 12 carbon atoms or vinyl ethers such as vinyl methyl ether and optionally small amounts of a crosslinking agent are used as customary thickeners or viscosity regulators .
  • Such copolymers are described, for example, in EP-A 328 725 (1) and EP-A 435 066 (2).
  • Copolymers of unbranched ⁇ -olefins having 8 to 30 carbon atoms and (meth) acrylic acid are known from US Pat. No. 3,755,272 (3). These copolymers are suitable for the production of electrocoating, water-soluble paints, floor coatings and textile treatment agents.
  • EP-A 047 009 (4) relates to copolymers of 70 to 93% by weight of partially or fully neutralized acrylic acid, 7 to 30% by weight of an ⁇ -olefin having 6 to 18 C atoms and optionally small amounts of a crosslinking agent. These copolymers are used as water-absorbing material in the form of, for example, films, fibers or fabrics in the medical and personal care sector. The copolymer is also recommended as a flocculant in water treatment.
  • EP-A-0 335 624 describes suitable surface-active polymers as thickeners which consist of 0.5 to 50% by weight of ionic, nonionic or ampholytic ⁇ , ⁇ -unsaturated monomers which have at least one aliphatic or araliphatic lipophilic group with C 8 -C 30 C atoms, and 40-99 wt .-% of other non-lipophilic ⁇ , ⁇ -unsaturated monomers.
  • the lipophilic monomers are predominantly ionic monomers, but also nonionic (meth) acrylic esters or allyl ether compounds.
  • the thickeners or viscosity regulators known from the prior art have a number of disadvantages. So these agents are often not sufficiently stable to hydrolysis and tend to decompose under the conditions of use. Some of these agents have a not inconsiderable toxic potential, which is of particular importance for cosmetic use.
  • the stability of the cosmetic preparations produced with these agents, in particular emulsions, is also often not yet optimal; above all, the stability towards electrolytes is in need of improvement.
  • the object of the present invention was therefore to provide new thickeners and dispersants for cosmetic preparations which no longer have the disadvantages of the prior art described.
  • component A Particularly suitable as component A are acrylic acid, methacrylic acid or maleic anhydride, but also crotonic acid, 2-pentenoic acid, maleic acid, fumaric acid or itaconic acid.
  • Long-chain compounds with isolated CC multiple bonds B include those with isolated acetylenic triple bonds and in particular those with isolated olefinic bonds Understand double bonds. “Isolated” is to be understood to mean that if there are several such CC multiple bonds, these are not conjugated and also do not interact with functional groups with ⁇ electron systems, for example carboxyl or carbonyl groups.
  • Long-chain carboxylic acids (1) for component B are, in particular, naturally occurring unsaturated fatty acids, for example oleic acid, nervonic acid, ⁇ -hydroxynervonic acid, elaidic acid, erucic acid, stearolic acid, palmitoleic acid, vaccenic acid, linoleic acid, linolenic acid, petroselinic acid, arachidonic acid or ricinoleic acid. Of these, C 14 to C 24 monocarboxylic acids with 1 to 4 CC multiple bonds, in particular olefinic double bonds, are preferred.
  • the carboxylic acids (1) can be used in the acid form or as alkali metal salts, in particular sodium or potassium salts, or as alkaline earth metal salts, in particular as calcium salts.
  • the long-chain carboxylic acid esters (1) used are the C 1 -C 4 -alkyl esters such as the methyl, ethyl, n-propyl, n-butyl or tert-butyl esters, for example methyl oleic acid, and the long-chain C 14 - bis esters C 24 alcohols with 1 to 4 CC multiple bonds, in particular olefinic double bonds, such as oleic acid oleyl esters, sorbitan esters such as sorbitan mono- or sorbitan sesquioleate, and the glycerol and polyglycerol esters, for example mono-, di- and triglycerides such as glycerol trioleate, including naturally occurring fats (lipids) .
  • C 1 -C 4 -alkyl esters such as the methyl, ethyl, n-propyl, n-butyl or tert-butyl esters, for example methyl
  • Amides from the carboxylic acids described and numerous amines for example oleic acid diethanolamide, isopropanolamide or dibutylamide, are also suitable.
  • Suitable long-chain amines (2) for component B are, in particular, aliphatic primary C 14 to C 24 amines with 1 to 4 CC multiple bonds, in particular olefinic double bonds, for example oleylamine.
  • the long-chain alcohols (3) used for component B are primarily primary C 14 -C 24 -alcohols with 1 to 4 CC multiple bonds, in particular olefinic double bonds, and esters thereof with saturated C 1 -C 4 -monocarboxylic acids such as formic acid, acetic acid, propionic acid or butyric acid.
  • Examples of (3) are oleyl alcohol and oley acetate.
  • Oils of natural origin in particular oils of vegetable origin, as well as natural waxes and animal tallow, fats and lard, which contain the mentioned compounds (1) to (3), are also very suitable as component B.
  • Suitable examples of this are coconut, palm kernel, palm, peanut, soybean, turnip, sunflower, igoba, olive, sesame, cottonseed, linseed, safflower, corn, castor or fish oil .
  • Suitable long-chain terminal and medium-sized alkenes (4) are in particular terminal C 16 -C 24 -alkenes ( ⁇ -olefins).
  • Examples of (5) are 1-hexadecene, 1-octadecene, 1-eicosaene, 1-tetracosene and C 20 / C 24 and C 20 / C 30 mixtures or cuts of the corresponding olefin fractions.
  • Suitable further copolymerizable monomers C for slight modification of the copolymers used according to the invention are, for example, N-vinylpyrrolidone, N-vinylcaprolactam, C 1 - to C 18 -alkyl (meth) acrylates, for example methyl (meth) acrylate, ethyl (meth) acrylate or stearyl (meth) acrylate, (meth) acrylamide or N- (C 1 - to C 18 -alkyl) (meth) acrylamides, for example N, N-dimethyl (meth) acrylamide, N-tert-butyl (meth) acrylamide or N -tert.-octyl (meth) acrylamide, vinyl ester of C 1 -C 18 carboxylic acids, for example vinyl acetate, vinyl propionate, vinyl versatic acid, hydroxyalkylene mono (meth) acrylic ester with two to six carbon atoms in the alkylene chain
  • the crosslinker component D used is olefinically polyunsaturated compounds such as, in particular, divinylbenzene, divinylethyleneurea, diallyltartaric acid diamide, methylenebisacrylamide, (meth) acrylic esters of polyfunctional alcohols such as trimethylolpropane, pentaerythritol, alkylene glycols having 2 to 6 carbon atoms in the alkylene group, polypropylene glycols, polyethylene glycols (Meth) acrylic acid, oleyl (meth) acrylate, oleyl (meth) acrylamide, trivinylcyclohexane, triallyltriazinetrione and allyl ether of trimethylolpropane, pentaerythritol and sucrose with at least two allyl ether units per molecule. Pentaerythritol triallyl ether, pentaallylsucrose, allyl methacrylate, trimethylolpropan
  • the monomers A to D can in principle be polymerized by all known processes.
  • a particularly suitable production method is precipitation polymerization, in which the monomers, but not the polymer, are soluble in the solvent system used.
  • Suitable solvents are aromatic such as toluene or xylene, halogenated such as 1,1,1-trichloroethane or methylene chloride and in particular semipolar solvents such as ketones with 3 to 6 C atoms and C 2 - to C 6 -alkyl esters of formic and acetic acid, furthermore non-polar Hydrocarbons, such as cyclohexane or petroleum ether and mixtures of these solvents.
  • Aromatic and aliphatic hydrocarbons with 5 to 12 carbon atoms in the molecule are also particularly suitable.
  • Suitable initiators are, for example, diacyl peroxides such as dilauroyl, didecanoyl and dioctanoyl peroxide or peresters such as tert-butyl peroctanoate, tert-butyl perpivalate, tert-amyl perpivalate or tert-butyl perneodecanoate as well as azo compounds such as dimethyl-2,2'-azyrate (isobutyl) 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile) or 2,2'-azobis (2,4-dimethylvaleronitrile).
  • diacyl peroxides such as dilauroyl, didecanoyl and dioctanoyl peroxide or peresters
  • tert-butyl peroctanoate tert-butyl perpivalate, tert-amyl perpiva
  • the polymerization mixture can contain water, alcohols, protective colloids, emulsifiers or even larger amounts of a base, e.g. Potassium carbonate can be added. If desired, the molecular weight of the polymers can be reduced by adding regulators to the polymerization mixture.
  • a base e.g. Potassium carbonate
  • the polymerization process is preferably controlled so that the polymer is obtained in the form of a finely divided powder which is optionally subjected to a suitable separation, drying or grinding process.
  • the aim of the use of the copolymers described according to the invention is above all to use these substances as thickeners, gel formers and as emulsifiers for technical, pharmaceutical and in particular cosmetic applications, for example in creams, lotions or gels.
  • the copolymers described are well suited for thickening aqueous systems to form thickened gels after the dispersed polymer has been added by adding a base such as e.g. Triethanolamine, NaOH, KOH, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, diisopropanolamine or tetrahydroxypropylethylenediamine have been sufficiently neutralized.
  • a base such as e.g. Triethanolamine, NaOH, KOH, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, diisopropanolamine or tetrahydroxypropylethylened
  • the polymers can be used to produce very stable emulsions from a water and an oil phase, in particular oil-in-water emulsions. Compared to conventional emulsifiers, lower amounts of the polymer are generally sufficient to obtain permanently stable emulsions.
  • the present invention furthermore relates to cosmetic preparations which contain the copolymers used according to the invention as thickening or dispersing agents in the amounts customary for this, that is to say about 0.05 to 2% by weight.
  • the copolymers used according to the invention have a number of advantages. Due to the chemical nature of the long-chain comonomers B, the hydrophobic portions of the polymer cannot be removed hydrolytically; the special one The thickening and dispersing effect is therefore retained even under strongly hydrolytic conditions.
  • the comonomers B also have a significantly lower toxic potential than, for example, the acrylate compounds known as comonomers from the prior art.
  • the gel viscosity 1.0 g of the polymer was dispersed in 190 ml of water in a beaker. 10 ml of a 10% triethanolamine solution were added with stirring. The viscosity of the gel obtained was determined to be 8.0 Pa.s using a hand-held viscometer (Hake VT-02). By spreading on a glass plate, one could see that the gel was smooth and almost speck-free.
  • emulsifiability 0.4 g of the polymer was weighed into a beaker and dispersed in 30 ml of paraffin oil. Then 100 ml of water and then 4 ml of a 10% triethanolamine solution were added with vigorous stirring. The emulsion was homogenized with a dispersing unit at 8000 rpm for a few seconds. The viscosity was determined to be 17.6 Pa.s as above. The structure of the emulsion was examined after 1 h by spreading on a glass plate. To determine the long-term stability, the emulsion was filled into a 100 ml standing cylinder and evaluated after 14 d. The emulsion showed no tendency to separate at this point.
  • the gel viscosity 1.0 g of the polymer was dispersed in 190 ml of water in a beaker. 10 ml of a 10% triethanolamine solution were added with stirring. The viscosity of the gel obtained was determined to be 8.0 Pa.s using a hand-held viscometer (Hake VT-02). By spreading on a glass plate, one could see that the gel was smooth and almost speck-free.
  • emulsifiability 0.4 g of the polymer was weighed into a beaker and dispersed in 30 ml of paraffin oil. Then 100 ml of water and then 4 ml of a 10% triethanolamine solution were added with vigorous stirring. The emulsion was homogenized with a dispersing unit at 8000 rpm for a few seconds. The viscosity was determined to be 7.6 Pa.s as above. The structure of the emulsion was examined after 1 h by spreading on a glass plate. To determine the long-term stability, the emulsion was filled into a 100 ml standing cylinder and evaluated after 14 d. The emulsion showed no tendency to separate at this point.
  • the gel viscosity 1.0 g of the polymer was dispersed in a beaker in 190 ml of water. 10 ml of a 10% triethanolamine solution were added with stirring. The viscosity of the gel obtained was determined to be 10.0 Pa.s using a hand-held viscometer (Hake VT-02). By spreading on a glass plate, one could see that the gel was smooth and almost speck-free.
  • emulsifiability 0.4 g of the polymer was weighed into a beaker and dispersed in 30 ml of paraffin oil. Then 100 ml of water and then 4 ml of a 10% triethanolamine solution were added with vigorous stirring. The emulsion was homogenized with a dispersing unit at 8000 rpm for a few seconds. The viscosity was determined to be 8.0 Pa.s as above. The structure of the emulsion was examined after 1 h by spreading on a glass plate. To determine the long-term stability, the emulsion was filled into a 100 ml standing cylinder and evaluated after 14 d. The emulsion showed no tendency to separate at this point.

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Abstract

Utilisation de copolymérisats obtenus par polymérisation amorcée par des radicaux, de A) 50 à 99,9 % en poids d'un acide monocarboxylique en C3 à C5 oléfiniquement insaturé, d'un acide dicarboxylique en C4 à C8 oléfiniquement insaturé ou de son anhydride, ou d'un mélange de tels acides ou anhydrides carboxyliques avec B) 0,1 à 50 % en poids d'un ou de plusieurs composés à chaînes longues à liaisons multiples C-C isolés appartenant à l'un des groupes suivants: 1) acides monocarboxyliques en C8 à C30 monoinsaturés ou polyinsaturés pouvant porter des groupes hydroxyle supplémentaires, ainsi que leurs sels de métaux alcalins et alcalino-terreux, leurs alkyesters, amides, sorbitane-esters, esters glycériniques et polyglycérimiques, 2) amines aliphatiques en C8 à C30 monoinsaturées ou polyinsaturées, 3) alcools en C8 à C30 monoinsaturés ou polyinsaturés, ainsi que leurs esters avec des acides monocarboxyliques saturés en C1 à C4, 4) (alkyle en C8 à C30) vinyléthers pouvant contenir jusqu'à 25 motifs d'alkylène-oxyde, et 5) alcènes en C13 à C30 en position finale et en position centrale, C) 0 à 49,9 % en poids d'autres monomères copolymérisables, et D) 0 à 10 % en poids d'un ou plusieurs composés renfermant au moins deux groupes oléfiniquement insaturés dans leur molécule et utilisés comme agents de réticulation, comme épaississants ou comme dispersants, notamment dans des préparations cosmétiques et pharmaceutiques.

Claims (8)

  1. Utilisation de copolymères qui peuvent être obtenus par la polymérisation amorcée par voie radicalaire de
    A) 75 à 99,45% en poids d'un acide monocarboxylique en C3 à C5, oléfiniquement insaturé, d'un acide dicarboxylique en C4 à C8, oléfiniquement insaturé, ou de son anhydride, ou d'un mélange de tels acides carboxyliques ou anhydrides d'acides carboxyliques avec
    B) 0,5 à 24,95% en poids d'un ou plusieurs composés à longues chaînes avec de multiples liaisons C-C, appartenant au groupe formé par
    (1) des acides monocarboxyliques en C8 à C30, mono- ou polyinsaturés, qui peuvent porter des radicaux hydroxyle complémentaires, ainsi que leurs sels de métaux alcalins et de métaux alcalino-terreux, leurs esters alkyliques, leurs amides, leurs esters avec le sorbitan, leurs esters avec la glycérine, ou leurs esters avec des polyglycérines,
    (2) des amines aliphatiques en C8 à C30, mono- ou polyinsaturées,
    (3) des alcools en C8 à C30 mono- ou polyinsaturés, ainsi que leurs esters avec des acides monocarboxyliques en C1 à C4 saturés,
    (4) des alcènes en C16 à C30 terminaux ou médians,
    C) 0 à 24,45% en poids d'autres monomères copolymérisables et
    D) 0,05 à 5% en poids d'un ou plusieurs composés comportant au moins deux radicaux oléfiniquement insaturés dans la molécule comme agents de réticulation,
    à titre d'agents épaississants ou dispersifs.
  2. Utilisation de copolymères suivant la revendication 1, en vue de la préparation desquels on a utilisé, à titre de composant A, de l'acide acrylique, de l'acide méthacrylique, ou de l'anhydride d'acide maléique.
  3. Utilisation de copolymères suivant les revendications 1 et 2, en vue de la préparation desquels on a mis en oeuvre, à titre de composant B), un ou plusieurs composés à longues chaînes avec des doubles liaisons oléfiniques isolées, appartenant au groupe formé par
    (1) des acides monocarboxyliques en C14 à C24, mono- à quadri insaturés, ainsi que leurs sels avec des métaux alcalins et des métaux alcalino-terreux, leurs esters alkyliques en C1 à C4, leurs esters avec la glycérine, ou leurs esters avec des polyglycérines,
    (2) des amines en C14 à C24 primaires aliphatiques, mono- à quadri insaturées,
    (3) des alcools en C14 à C24 primaires, mono- à quadri insaturés, ainsi que leurs esters avec des acides monocarboxyliques en C1 à C4 saturés,
    (4) des alcènes en C16 à C24 terminaux.
  4. Utilisation de copolymères suivant l'une quelconque des revendications 1 à 3, en vue de la préparation desquels on a utilisé, à titre de composant D, l'éther allylique de la pentaérythrite, le triméthylolpropane, ou le saccharose, avec au moins deux unités éther allylique dans la molécule, ainsi que le méthacrylate d'allyle, le (méth)acrylate d'oléyle, ou le méthylènebisacrylamide.
  5. Utilisation de copolymères suivant la revendication 1, à titre d'agents épaississants ou d'agents dispersifs dans des préparations cosmétiques.
  6. Utilisation de copolymères suivant la revendication 1, à titre d'agents épaississants ou d'agents dispersifs dans des préparations pharmaceutiques.
  7. Copolymères que l'on peut obtenir par la polymérisation amorcée par voie radicalaire de
    (A) 75 à 99,45% en poids d'un acide monocarboxylique en C3 à C5, oléfiniquement insaturé, d'un acide dicarboxylique en C4 à C8, oléfiniquement insaturé, ou de son anhydride, ou d'un mélange de tels acides carboxyliques ou anhydrides d'acides carboxyliques avec
    (B) 0,5 à 24,95% en poids d'un ou plusieurs composés à longues chaînes avec de multiples liaisons C-C, appartenant au groupe formé par
    (1) des acides monocarboxyliques en C8 à C30, mono- ou polyinsaturés, qui peuvent porter des radicaux hydroxyle complémentaires, ainsi que leurs sels de métaux alcalins et de métaux alcalino-terreux, leurs esters alkyliques en C1 à C4, leurs amides, leurs esters avec le sorbitan, leurs esters avec la glycérine, ou leurs esters avec des polyglycérines,
    (2) des amines aliphatiques en C8 à C30, mono- ou polyinsaturées,
    (3) des alcools en C8 à C30 mono- ou polyinsaturés, ainsi que leurs esters avec des acides monocarboxyliques en C1 à C4 saturés,
    C) 0 à 24,45% en poids d'autres monomères copolymérisables et
    D) 0,05 à 5% en poids d'un ou plusieurs composés comportant au moins deux radicaux oléfiniquement insaturés dans la molécule comme agents de réticulation, à titre d'agents épaississants ou dispersifs.
  8. Préparations cosmétiques ou pharmaceutiques qui contiennent des copolymères suivant l'une quelconque des revendications 1 à 4, à titre d'agents épaississants et d'agents dispersifs en les proportions habituelles, à cette fin.
EP93911463A 1992-04-23 1993-04-14 Utilisation de copolymerisats d'acides carboxyliques et de composes a chaines longues a liaisons multiples c-c isolees comme epaississants ou comme dispersants Expired - Lifetime EP0637321B1 (fr)

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Application Number Priority Date Filing Date Title
DE4213283 1992-04-23
DE4213283A DE4213283A1 (de) 1992-04-23 1992-04-23 Verwendung von Copolymerisaten aus Carbonsäuren und langkettigen Verbindungen mit isolierten C-C-Mehrfachverbindungen als Verdickungs- oder Dispergiermittel
PCT/EP1993/000903 WO1993022357A1 (fr) 1992-04-23 1993-04-14 Utilisation de copolymerisats d'acides carboxyliques et de composes a chaines longues a liaisons multiples c-c isolees comme epaississants ou comme dispersants

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EP0637321A1 EP0637321A1 (fr) 1995-02-08
EP0637321B1 true EP0637321B1 (fr) 1997-07-09

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US (1) US7465774B1 (fr)
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JP (1) JP3180814B2 (fr)
DE (2) DE4213283A1 (fr)
ES (1) ES2103473T3 (fr)
WO (1) WO1993022357A1 (fr)

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DE19600324A1 (de) 1996-01-08 1997-07-10 Basf Ag Granulate für kosmetische und pharmazeutische Zubereitungen
DE19811919A1 (de) * 1998-03-18 1999-09-23 Basf Ag Verwendung von Copolymerisaten monoethylenisch ungesättigter Carbonsäuren als Solubilisatoren
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JP3180814B2 (ja) 2001-06-25
DE59306889D1 (de) 1997-08-14
JPH07505917A (ja) 1995-06-29
ES2103473T3 (es) 1997-09-16
DE4213283A1 (de) 1993-10-28
EP0637321A1 (fr) 1995-02-08
WO1993022357A1 (fr) 1993-11-11
US7465774B1 (en) 2008-12-16

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